Single‐Site Nickel‐Anchored Photosensitive Covalent Organic Framework for Metallaphotocatalytic C─S/C─N Cross‐Coupling Reactions
Abstract
ABSTRACT The development of multifunctionally heterogeneous catalysts, simultaneously bearing photosensitizer and nonnoble metal catalyst in close spatial proximity, represents a promising solution for promoting metallaphotoredox‐mediated catalysis, albeit it remains challenging. Herein, a single‐site Ni‐functionalized photosensitive covalent organic framework (COF), TTA‐BPyDA(Ni)‐COF, has been constructed by implementing a postsynthetic metallization strategy in a triazine‐based COF scaffold. The precise integration of photosensitizer and Ni‐catalytic active centers within TTA‐BPyDA(Ni)‐COF not only dramatically improves the metallaphotocatalytic (MPC) performance in C─S/C─N cross‐coupling reaction between diverse thiols/amines and aryl iodides with electron‐rich/neutral/deficient groups but also confers TTA‐BPyDA(Ni)‐COF with outstanding recyclability and durability compared with its homogeneous counterpart. Importantly, the MPC C─S/C─N reaction mechanisms have been well established by comprehensive experimental and theoretical simulations. This work offers valuable insights for developing single‐site nonnoble metal‐functionalized COF catalytic platforms that integrate photoredox centers with catalytic transition‐metal cores.
Article Details
Authors (13)
Yang‐Yang Xiong
GBRCE For Functional Molecular Engineering, Lehn Institute of Functional Materials, IGCME, School of Chemistry Sun Yat‐Sen University Guangzhou China
Songlin Deng
GBRCE for Functional Molecular Engineering, Lehn Institute of Functional Materials, IGCME, School of Chemistry
Haiping Wang
State Key Laboratory of Integrated Management of Pest Insects and Rodents, Institute of Zoology, Chinese Academy of Sciences
Shi‐Hua Liu
GBRCE For Functional Molecular Engineering, Lehn Institute of Functional Materials, IGCME, School of Chemistry Sun Yat‐Sen University Guangzhou China
Peter VanNatta
Department of Chemistry
Jie‐Li Lin
GBRCE For Functional Molecular Engineering, Lehn Institute of Functional Materials, IGCME, School of Chemistry Sun Yat‐Sen University Guangzhou China
Juejing Liu
Department of Chemistry, Washington State University
Chengjun Sun
Advanced Photon Source
Xiaofeng Guo
Department of Chemistry, Washington State University
Cheng‐Xia Chen
GBRCE For Functional Molecular Engineering Lehn Institute of Functional Materials IGCME School of Chemistry Sun Yat‐Sen University Guangzhou P. R. China
Ayman Nafady
Department of Chemistry, College of Science
Abdullah M. Al‐Enizi
Department of Chemistry, College of Science King Saud University Riyadh Saudi Arabia
Shengqian Ma
Department of Chemistry